Water-insoluble salts of phthalocyanine-sulphonic acids



Patented Nov. 23, 1937 WATER-INSOLUBLE SALTS OF PHTHALO-CYANINE-SULPHONIC ACIDS Karl Holzach and Georg Niemann,Ludwigshafen-on-the-Rhine, Germany, assignors to General Aniline Works,Inc., New York, N. Y., a corporation of Delaware No Drawing. Originalapplication April 18, 1936, Serial No. 75,234. Divided and thisapplication November 20, 1936, Serial No. 111,852. In Germany April 20,1935 3 Claims. (Cl. 134-585) The present invention relates towater-insoluble salts of phthalocyanine sulphonic acids. 7

By heating derivatives of aromatic ortho-dicarboxylic acids which areformed by the combination of nitrogen to the carbon atoms of the twoadjacent carboxylic groups, or their substitution products, such'asphthalodinitrile, ortho-cyanobenzamide or naphthalene ortho-dicarboxylicacid dinitrils, either alone or together with metals or metal compoundsor other substances, valuable colored products, the socalledphthalocyanines, are obtained which may be subsequently sulphonated whenthey do not already contain sulphonic groups.

We have now found that valuable water-insoluble salts of the sulphonicacids of the phthalo cyanines which hereinafter are called color lakes,can be obtained by treating, in aqueous solution, the said sulphonicacids with metal compounds suitable for laking, in particular solublemetal salts, metal oxides or metal hydroxides. The sulphonic acids, inthe form of their alkali metal salts, are soluble in water giving a deepblue coloration and are preferably employed as such according to thisinvention. Suitable metal compounds for laking are for example thesoluble salts, oxides and hydroxides of calcium, strontium, barium,magnesium, aluminium, iron, cobalt, zinc, manganese and nickel. In manycases it is advantageous to allow the laking to take place in thepresence of additional substances such as resin soaps, soluble syntheticresins or dispersing agents. Either a neutral, acid or alkaline mediummay be employed.

The following examples will further illustrate how the said inventionmay be carried out in practice but the invention is not restricted tothese examples. The parts are by weight.

Example 1 7 parts of the sodium salt of the sulphonic acid of the bluesubstance obtainable by heating phthalodinitrile in the presence ofcuprous chloride and pyridine (prepared by sulphonation of the bluesubstance with five times the amount of 30 per cent oleum while heatingfor an hour at 80 C., pouring onto ice and neutralizing by the additionof sodium carbonate with subsequent salting out) are dissolved in 100parts of water, heated and precipitated by the addition of 9 parts ofbarium chloride. A brilliant green-blue color lake is obtained.

A corresponding amount of calcium chloride or zinc chloride may beemployed instead of barium chloride. A similar procedure is followedwhen employing magnesium or manganese salts for the laking.

Example 2 parts of the sodium salt specified in Example 1 are added toan aqueous suspension of 200 parts of aluminium hydroxide. The brilliantblue alumina lake is isolated and dried in the usual manner.

Example 3 parts of heavy spar are suspended in a solution of 10 parts ofaluminium sulphate and 5 parts of soda in 135 parts of water and mixedwith a solution of 12 parts of barium chloride in 88 parts of water. Theprecipitate is washed by repeatedly spraying it with water and decantingand suspended in a solution of 1.5 parts of the sulphonic acid of copperphthalocyanine (of. Example 1) and 1.5 parts of the azo dyestufi fromdiazotized. 1.2.5-aniline-sulphonic acid and 1(2 5-disulphophenyl)5-pyraZolone-3-carboxylic acid in 300 parts of water. The dyestufi isprecipitated by adding a solution of 3 parts of barium chloride in 30parts of water. The color paste separated by filtration may be brushedon Wall paper together with vegetable glue, a fast, brilliant greenpaint-'- ing being obtained.

More greenish color shades are obtained if instead of acopper-phthalocyanine-sulphonic acid, a sulphonic acid of thephthalocyanine free from metal is employed.

Example 4 2 parts of the sodium salt of thenickel-phthalocyanine-sulphonic acid prepared by causing 300 parts of 33per cent oleum to act on 30 parts of a nickel-phthalocyanine (obtainableby heating ortho-phthalodinitrile and nickelous chloride in the presenceof quinoline at between 200 and 210 C. for several hours) at C. within 2hours, are dissolved in 1000 parts of water. To this solution there isadded a precipitate freshly prepared from 20 parts of barium sulphate,10 parts of a 10 per cent aqueous solution of aluminium sulphate, 5parts of an about 10 per cent aqueous solution of sodium carbonate and12 parts of an about 10 per cent aqueous solution of barium chloride.

The color lake is then precipitated on the substratum by the addition of3 parts of barium chloride. The color paste obtained yields a brilliantgreen-blue coating.

Example 5 A zincphthalocyanine-sulphonic acid oband kept at C. for24hours.

tained by treating parts of zinc-phthalocya- 1 nine prepared for exampleby heating orthophthalodinitrile'with zinc oxide and formamide with300parts of '33 per cent'oleum at 50 C. Within minutes is made into alake lnthe manner described in Example 4. A brilliant green color lakeis. thus obtained.

Example 6 V a i 100 parts of copper phthaloc yani'neare entered into amixture of 500 parts of sulphuric acid 2.3 dicyan naphthalene[ isconverted into a phthalocyanine by heating it with a mixture ofnitrobenzene, pyridine and cuprous chloride. The a resulting dyestufi issulphonated by treating it i with 30 per cent oleum at room temperature.

- The sodium salt ofthis sulphonic acid which is readily soluble inwater is made into a lake in the manner similar to that of Example 4. Abrilliant green color lake is thus obtained which is 7 especiallysuitable for coloring wall papers;

Example 8 100 parts of a 2 per cent aqueous solution of the sodium saltof the metal-free phthalocyaninesulphonic acid obtained by sulphonatingthe metal-.free phthalocyanine (obtainable from ortho-phthalodinitrile)in 30 per cent oleum at about 70 C. are mixed with 5 parts of a 10 percent solution of resin soap and precipitated with 5'parts by weight of a10 per cent solutionof barium chloride, a brilliant'green color lakethus being obtained. 7

Example 9 30 parts of heavy spar are made im 'a paste with 10 parts of a10 per cent aqueous solution of aluminium sulphate which latter istransformed into aluminium hydroxide by the addition of 5 parts of a 10per cent aqueous solution of an stratum ofheavy spar, aluminiumhydroxide and copperphthalocyanine are added to the said subblanc fixe,the said substratum having been care: 7

fully washed, and the pigment is precipitated by means of lparts of a 10per cent aqueous solution of barium chloride. A color lake having abrilliant Bremen blue. color shade is thus obtained.

Instead of barium chloride there may also be employed a correspondingamount of calcium chloride or zinc chloride as well as of salts of othermetals, such as aluminium sulphate.

- Instead of the said substratum other substrata usual in the colorlakeindustry may also'be used, such as lithopone, zinc white or calcspar. V

This application has been divided out from our copending applicationSer. No. 75,234, filed April18, 1936. I

What we claim is:

l. A color lake composition comprising a substratum and awater-insoluble metal salt of' a phthalocyanine sulphonic acid.

' 2. A color lake composition comprising a substratum and awater-insoluble metal salt of a phthalocyanine sulphonic acid and adispersing. agent.

3. A color lake composition comprising a substratum and aWater-insoluble metal salt of a phthalocyanine sulphonic acid and aresin soap.

' KARL HOLZACH. f

GEORG NIEMANN.

